WO2020111644A1 - Composition de copolymère bloc, son procédé de production et composition d'asphalte la contenant - Google Patents

Composition de copolymère bloc, son procédé de production et composition d'asphalte la contenant Download PDF

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Publication number
WO2020111644A1
WO2020111644A1 PCT/KR2019/015945 KR2019015945W WO2020111644A1 WO 2020111644 A1 WO2020111644 A1 WO 2020111644A1 KR 2019015945 W KR2019015945 W KR 2019015945W WO 2020111644 A1 WO2020111644 A1 WO 2020111644A1
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Prior art keywords
block
copolymer
composition
weight
block copolymer
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PCT/KR2019/015945
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English (en)
Korean (ko)
Inventor
이세경
김태중
김현우
이성두
이춘화
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주식회사 엘지화학
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Priority claimed from KR1020190139439A external-priority patent/KR102241925B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2020545475A priority Critical patent/JP6995213B2/ja
Priority to US16/978,062 priority patent/US11203687B2/en
Priority to EP19891032.5A priority patent/EP3744787B1/fr
Priority to CN201980017218.9A priority patent/CN111819241B/zh
Publication of WO2020111644A1 publication Critical patent/WO2020111644A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch

Definitions

  • the present invention relates to a block copolymer composition, and more particularly, to a block copolymer composition for use as an asphalt modifier, a manufacturing method thereof, and an asphalt composition comprising the same.
  • Asphalt is a residue after most of the volatile oil in the petroleum oil component evaporates, and maintains a highly viscous liquid or semi-solid at high temperatures, but has properties of hardening at temperatures below room temperature.
  • asphalt since asphalt is rich in plasticity, has great waterproofness, electrical insulation, adhesiveness, and has chemically stable characteristics, it is widely applied to building materials such as road pavement and waterproofing materials.
  • such asphalt has a problem that plastic deformation occurs when exposed to high temperatures for a long time during use, and cracks are generated by external impacts at low temperatures.
  • a vinyl aromatic hydrocarbon-conjugated diene copolymer such as a styrene-butadiene-styrene (SBS) copolymer
  • SBS styrene-butadiene-styrene
  • the softening point of the asphalt composition including a diblock copolymer terminal-modified in the block copolymer composition used as an asphalt modifier And improving solubility at the same time.
  • the present invention is to provide a block copolymer composition usable as an asphalt modifier, and when modifying the asphalt using the block copolymer composition, an object of the present invention is to provide an asphalt composition with improved softening point and solubility.
  • the present invention is a block copolymer composition
  • a diblock copolymer and a triblock copolymer the diblock copolymer is a first conjugated diene-based monomer
  • a block comprising a first block comprising a derived repeating unit and a second block comprising a repeating unit derived from a first vinyl aromatic monomer, and a functional group derived from a modified initiator represented by Formula 1 below at one end of the diblock copolymer
  • a copolymer composition is provided.
  • R 1 is a hydrocarbyl group having 1 to 20 carbon atoms
  • R 2 is an alkylene group having 1 to 30 carbon atoms
  • R 3 and R 4 are each independently hydrogen or 1 to 30 carbon atoms. It is an alkyl group.
  • the present invention in the presence of a denaturation initiator represented by the following formula (1), preparing a first block comprising a repeating unit derived from a first conjugated diene-based monomer; Preparing a diblock copolymer by polymerizing a second block including a repeating unit derived from a first vinyl aromatic monomer in the presence of the first block prepared in the above step; Preparing a triblock copolymer; And it provides a method for producing a block copolymer composition comprising the step of mixing the diblock copolymer and the triblock copolymer.
  • a denaturation initiator represented by the following formula (1)
  • R 1 is a hydrocarbyl group having 1 to 20 carbon atoms
  • R 2 is an alkylene group having 1 to 30 carbon atoms
  • R 3 and R 4 are each independently hydrogen or 1 to 30 carbon atoms. It is an alkyl group.
  • the present invention provides an asphalt composition comprising the block copolymer composition and asphalt.
  • the block copolymer composition according to the present invention When used as an asphalt modifier, it has an effect of simultaneously improving the softening point and solubility of the asphalt composition to excellent levels.
  • the terms'derived repeating unit','derived functional group' and'derived linking group' may refer to a component, structure, or the substance itself originating from a substance, and in a specific example,'derived repeating unit' is a polymerization of a polymer
  • the monomer to be introduced may mean a repeating unit formed in the polymer by participating in the polymerization reaction
  • 'derived functional group' refers to a repeating unit formed in the polymer by participating in the polymerization reaction during the polymerization of the polymer. It may mean a functional group connected to one end
  • 'derived linking group' means a linking group that connects each polymer in the coupled polymer by introducing the coupling agent into the coupling reaction during the coupling reaction between the polymers. May be
  • the term'block' may mean a group of repeating units composed of only repeating units derived from the same monomer, only the same monomers participating in the polymerization reaction in the copolymer, and specific examples include repeating units derived from vinyl aromatic monomers.
  • the block may mean a block formed of only repeating units derived from a vinyl aromatic monomer, and a block including a repeating unit derived from a conjugated diene-based monomer may mean a block formed only of repeating units derived from a conjugated diene-based monomer. .
  • the terms'diblock copolymer' and'triblock copolymer' may mean a copolymer comprising two or more blocks derived from different monomers.
  • the term'active polymer' is a polymer formed by an anionic polymerization reaction, and one end of the polymer may mean a polymer capable of additional polymerization or reaction by maintaining an anionic state, and specifically, a living anionic polymer. have.
  • the term'solution' is in the form of dispersing or dissolving polymers, diblock copolymers and block copolymers produced by polymerization or coupling reaction of each step of the method for preparing a block copolymer composition in a hydrocarbon-based solvent. It can mean what it contains.
  • the block copolymer composition according to the present invention may include a diblock copolymer and a triblock copolymer.
  • the vinyl aromatic-conjugated diene block copolymer mainly used as an asphalt modifier especially in the styrene-butadiene-styrene (SBS) triblock copolymer, the content between the styrene block and the butadiene block, the vinyl group present in the conjugated diene block Factors related to the microstructure of molecules, such as the content of, are correlated with each other, and when the high temperature property increases, the low temperature property decreases, when the dissolution rate increases, the mechanical property decreases, and when the sulfur is crosslinked, a gel is formed in the asphalt composition Can cause problems.
  • SBS styrene-butadiene-styrene
  • the block copolymer composition according to the present invention includes a triblock copolymer and a diblock copolymer containing a functional group derived from a modified initiator at one end at the same time, so that an additive is added or the molecular weight of the triblock copolymer is adjusted. Or, there is an effect of improving the softening point and solubility without changing the molecular microstructure.
  • the diblock copolymer included in the block copolymer composition according to the present invention includes a first block comprising a repeating unit derived from a first conjugated diene-based monomer and a second block comprising a repeating unit derived from a first vinyl aromatic monomer, , It may be to include a functional group derived from a modified initiator represented by the following formula (1) at one end of the diblock copolymer. Meanwhile, the one end may be one end of the first block of the diblock copolymer.
  • R 1 is a hydrocarbyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, or 2 to 8 carbon atoms
  • R 2 is 1 to 30 carbon atoms, 1 to 20 carbon atoms, and 1 to 20 carbon atoms. It is an alkylene group having 8 carbon atoms
  • R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or an alkyl group having 1 to 8 carbon atoms.
  • the first block including the repeating unit derived from the first conjugated diene-based monomer of the diblock copolymer may be a block formed by polymerization of the first conjugated diene-based monomer.
  • the first conjugated diene-based monomer for forming the first block is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2 It may be one or more selected from the group consisting of -phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom).
  • the content of the repeating unit derived from the first conjugated diene-based monomer may be 60 parts by weight to 80 parts by weight, 65 parts by weight to 75 parts by weight, or 67 parts by weight to 73 parts by weight based on 100 parts by weight of the total diblock copolymer have.
  • a block copolymer composition containing a diblock copolymer within this range as an asphalt modifier, there is an effect of improving the softening point and solubility of the asphalt composition.
  • the second block including the repeating unit derived from the first vinyl aromatic monomer of the diblock copolymer may be a block formed by polymerization of the first vinyl aromatic monomer.
  • the first vinyl aromatic monomer for forming the second block is styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- It may be one or more selected from the group consisting of (p-methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene.
  • the content of the repeating unit derived from the first vinyl aromatic monomer may be 20 parts by weight to 40 parts by weight, 25 parts by weight to 35 parts by weight, or 27 parts by weight to 33 parts by weight based on 100 parts by weight of the diblock copolymer. .
  • a block copolymer composition containing a diblock copolymer within this range as an asphalt modifier, there is an effect of improving the softening point and solubility of the asphalt composition.
  • one end of the diblock copolymer specifically, the modification represented by Formula 1 below at one end of the first block And initiator-derived functional groups.
  • R 1 is a hydrocarbyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, or 2 to 8 carbon atoms
  • R 2 is 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 1 carbon atom
  • It is an alkylene group having 8 carbon atoms
  • R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or an alkyl group having 1 to 8 carbon atoms.
  • the denaturation initiator represented by Formula 1 may be represented by Formula 2 and Formula 3 below.
  • the denaturation initiator of the functional group derived from the denaturation initiator may be a denaturation initiator prepared by denaturation with a benzyl amine compound in order to improve the softening point and solubility of the asphalt composition.
  • the functional group derived from the benzyl amine-based compound is located at one end of the diblock copolymer, the affinity between the polar group present in the asphalt and the functional group derived from the denaturation initiator increases, and thus the asphalt of the diblock copolymer containing the same There is an effect to improve the solubility.
  • the improved solubility of the diblock copolymer also has an effect of improving the overall solubility of the block copolymer composition because it also aids in chain relaxation of the triblock copolymer contained together in the block copolymer composition.
  • a reaction between functional groups derived from the benzyl amine-based compound in the diblock copolymer may occur due to the high temperature (180° C. or higher) inside the asphalt.
  • the block copolymer is modified in the form of a triblock copolymer or a combination of several diblock copolymers, thereby increasing the polymer content and contributing to the improvement of physical properties. Therefore, when using a block copolymer containing a diblock copolymer containing a functional group derived from the modified initiator at one end as an asphalt modifier, there is an effect of improving the softening point and solubility of the asphalt composition.
  • the modified initiator may be a vinyl group substituted among benzyl amine-based compounds, which not only serves to initiate the polymerization reaction during the preparation of the diblock copolymer, but also hydrogen between functional groups derived from the modified initiator in the final step of the reaction. Interactions such as gelation, including binding, covalent bonding, and the like can be performed.
  • the modified initiator according to the present invention serves as an initiator, and the terminal of the diblock copolymer prepared using the same can be effectively modified. Therefore, even without the introduction of a coupling agent, in the modified asphalt manufacturing process, the modified form of the triblock copolymer or several diblock copolymers are combined in a modified form according to the interaction between the functional groups derived from the modified initiator, thereby increasing the polymer content and contributing to improving physical properties. It works. Accordingly, there is an excellent effect of compatibility with the components included in the asphalt composition and the softening point of the asphalt composition.
  • the content of the functional group derived from the denaturation initiator is.
  • the diblock copolymer may be 0.248 parts by weight to 0.322 parts by weight, 0.248 parts by weight to 0.32 parts by weight, or 0.25 parts by weight to 0.3 parts by weight based on 100 parts by weight of the total.
  • a block copolymer composition containing a diblock copolymer within this range as an asphalt modifier, there is an effect of improving the softening point and solubility of the asphalt composition.
  • the triblock copolymer included in the block copolymer composition according to the present invention is derived from a third block including a repeating unit derived from a second vinyl aromatic monomer, a fourth block including a repeating unit derived from a second conjugated diene monomer, and a coupling agent. It may include a linker.
  • the third block including the repeating unit derived from the second vinyl aromatic monomer of the triblock copolymer may be a block formed by polymerization of the second vinyl aromatic monomer.
  • the second vinyl aromatic monomer for forming the third block is styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- It may be one or more selected from the group consisting of (p-methylphenyl)styrene and 1-vinyl-5-hexylnaphthalene, and may be the same or different from the first vinyl aromatic monomer described above.
  • the content of the repeating unit derived from the second vinyl aromatic monomer may be 20 parts by weight to 40 parts by weight, 25 parts by weight to 35 parts by weight, or 27 parts by weight to 33 parts by weight based on 100 parts by weight of the triblock copolymer have.
  • a block copolymer composition containing a triblock copolymer within this range as an asphalt modifier, there is an effect of improving the softening point and solubility of the asphalt composition.
  • the fourth block including the repeating unit derived from the second conjugated diene-based monomer of the triblock copolymer may be a block formed by polymerization of the second conjugated diene-based monomer.
  • the second conjugated diene-based monomer for forming the fourth block is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2 -Phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom) may be at least one selected from the group consisting of, the same as the first conjugated diene monomer described above or It can be different.
  • the content of the repeating unit derived from the second conjugated diene-based monomer may be 60 parts by weight to 80 parts by weight, 65 parts by weight to 75 parts by weight, or 67 parts by weight to 73 parts by weight based on 100 parts by weight of the triblock copolymer. .
  • a block copolymer composition containing a triblock copolymer within this range as an asphalt modifier, there is an effect of improving the softening point and solubility of the asphalt composition.
  • the coupling agent-derived linking group may be a linking group connecting a block including a repeating unit derived from a plurality of second conjugated diene-based monomers.
  • the coupling agent for forming the coupling group derived from the coupling agent may be at least one selected from the group consisting of a vinyl group-containing hydrocarbon-based compound, an ester-based compound, a silane-based compound, a polysiloxane-based compound, and a polyketone.
  • the coupling agent is a polyfunctional coupling agent, a vinyl group-containing hydrocarbon-based compound such as divinylbenzene; Ester-based compounds such as diethyl adipate and glycidyl methacrylate; Silane compounds such as dimethyldichlorosilane, methyldichlorosilane, methoxysilane, glycidoxy trimethoxysilane, and oxydipropyl bis(trimethoxysilane); polysiloxane compounds such as ⁇ , ⁇ -bis(2-trichlorosilylethyl)polydimethylsiloxane; Or it may be one or more selected from the group consisting of polyketone.
  • a polyfunctional coupling agent a vinyl group-containing hydrocarbon-based compound such as divinylbenzene
  • Ester-based compounds such as diethyl adipate and glycidyl methacrylate
  • Silane compounds such as dimethyldichlorosilane,
  • the content of the coupling group derived from the coupling agent may be 0.278 parts by weight to 0.516 parts by weight, 0.28 parts by weight to 0.51 parts by weight, or 0.285 parts by weight to 0.45 parts by weight based on 100 parts by weight of the total triblock copolymer.
  • the coupling efficiency increases, and when a block copolymer composition including a triblock copolymer is used as an asphalt modifier, there is an effect of improving the softening point of the asphalt composition.
  • the content of the diblock copolymer may be 25 wt% to 42 wt%, 30 wt% to 40 wt%, or 30 wt% to 35 wt%, and the tree
  • the content of the block copolymer may be 58% to 75% by weight, 60% to 70% by weight, and 65% to 70% by weight.
  • the coupling efficiency of the block copolymer composition may be 62% to 79%, 62% to 73%, or 65% to 67%, within this range the block copolymer composition according to the present invention as an asphalt modifier It has the effect of improving the softening point and solubility of the asphalt composition.
  • Method for producing a block copolymer composition comprises the steps of preparing a diblock copolymer; Preparing a triblock copolymer; And mixing the diblock copolymer and the triblock copolymer.
  • the preparing of the diblock copolymer may include preparing a first block including a repeating unit derived from a first conjugated diene-based monomer in the presence of a denaturing initiator represented by Formula 1; And in the presence of the first block prepared in the step, polymerizing a second block including a repeating unit derived from a first vinyl aromatic monomer to prepare a diblock copolymer.
  • R 1 is a hydrocarbyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, or 2 to 8 carbon atoms
  • R 2 is 1 to 30 carbon atoms, 1 to 20 carbon atoms, and 1 to 20 carbon atoms. It is an alkylene group having 8 carbon atoms
  • R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or an alkyl group having 1 to 8 carbon atoms.
  • the modified initiator may be used by preparing a modified initiator represented by Formula 1 by reacting a polymerization initiator with a vinyl group-substituted benzyl amine compound.
  • R 1 is derived from a butyl group
  • R 2 is a methylene group
  • R 3 and R 4 are methyl groups, respectively.
  • R 1 when R 1 is derived from a butyl group, and R 2 is a methylene group, R 3 and R 4 are each hydrogen, the modification initiator is as follows.
  • n-butyllithium which is a polymerization initiator, the n-butyllithium is substituted at one end to form an active polymer benzyl amine compound.
  • n-butyl lithium methyl lithium, ethyl lithium, propyl lithium, s-butyl lithium, t-butyl lithium, hexyl lithium, n-decyl lithium, t-octyl lithium, phenyl lithium, 1-naphthyl lithium , n-ethylsilicium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, lithium Alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, lithium isopropylamide and the like can be used.
  • Preparation of the denaturation initiator according to the present invention is carried out for 5 minutes to 20 minutes, 5 minutes to 15 minutes, or 7 minutes to 12 minutes at a temperature of 50 °C to 70 °C, 53 °C to 68 °C or 58 °C to 62 °C Can be.
  • the reaction rate of the polymerization initiator and the vinyl group-substituted benzyl amine-based compound is fast, thereby facilitating the preparation of a modified initiator.
  • the molar ratio of the starting material and the polymerization initiator during the reaction for preparing the modified initiator may be 1:0.7 to 1.1 1:0.75 to 1.1 or 1:0.8 to 1.1. Within this range, the reaction rate of the polymerization initiator and the vinyl group-substituted benzyl amine-based compound is fast, thereby facilitating the preparation of a modified initiator.
  • a first conjugated diene-based monomer is added and polymerized to include a first monoblock polymer comprising a repeating unit derived from the first conjugated diene-based monomer. It may be a step of preparing a solution.
  • the first monoblock polymer solution prepared in the step of preparing the first block includes a polymer for forming a block including a repeating unit derived from a first conjugated diene-based monomer.
  • the step of preparing the diblock copolymer by polymerizing the second block comprises: a first monoblock polymer solution comprising a repeating unit derived from the first conjugated diene-based monomer prepared in the step of preparing the first block, the first By adding and polymerizing a vinyl aromatic monomer, a first diblock copolymer solution comprising a first block comprising a repeating unit derived from a first conjugated diene monomer and a second block comprising a repeating unit derived from a first vinyl aromatic monomer is obtained. It may be a manufacturing step.
  • the step of preparing the diblock copolymer by polymerizing the second block may be performed without input of a separate polymerization initiator. . That is, the second block is polymerized by a first vinyl aromatic monomer that is additionally injected from the living anionic polymer, followed by a repeating unit block derived from the first conjugated diene-based monomer, followed by a first input when polymerizing the second block. It may be a step for preparing a first diblock copolymer solution including a first diblock copolymer, in which a block according to a vinyl aromatic monomer is formed.
  • a third block including a repeating unit derived from a second vinyl aromatic monomer, a fourth block including a repeating unit derived from a second conjugated diene monomer, and a coupling group derived from a coupling agent It may be to include a step of preparing a triblock copolymer comprising.
  • the step of preparing the triblock copolymer may be performed separately from the step of preparing the diblock copolymer, and may be performed simultaneously or sequentially with the diblock copolymer.
  • the triblock copolymer includes a repeating unit derived from a second vinyl aromatic monomer by adding and polymerizing a second vinyl aromatic monomer in the presence of a common polymerization initiator that can be used in the art, in a hydrocarbon solvent.
  • a second conjugated diene-based monomer is added to the polymer solution for forming a third block including a repeating unit derived from a second vinyl aromatic monomer prepared in the step of preparing the second monoblock polymer solution, and then polymerized to obtain a second vinyl aromatic
  • Preparing a second diblock copolymer solution comprising a second diblock copolymer comprising a third block comprising a repeat unit derived from a monomer and a fourth block comprising a repeat unit derived from a second conjugated diene-based monomer;
  • a third block comprising a repeating unit derived from a second vinyl aromatic monomer, by adding
  • a polymerization unit of a triblock copolymer initiates polymerization to form a third block comprising a repeating unit derived from a second vinyl aromatic monomer, and a repeating unit derived from a second vinyl aromatic monomer. It may be a step for preparing a second monoblock polymer solution comprising a polymer for forming a third block comprising a.
  • the second monoblock polymer solution prepared in the step of preparing the second monoblock polymer solution may include a polymer for forming a block including a repeating unit derived from a second vinyl aromatic monomer.
  • the step of preparing the second diblock copolymer solution comprises a repeating unit derived from the second vinyl aromatic monomer contained in the second monoblock polymer solution prepared in the step of preparing the second monoblock polymer solution.
  • a second conjugated diene-based monomer is added and polymerized to form a third block comprising a repeating unit derived from a second vinyl aromatic monomer and a fourth block comprising a repeating unit derived from a second conjugated diene-based monomer. It may be a step for preparing a second diblock copolymer solution comprising a second diblock copolymer comprising blocks.
  • the second monoblock polymer solution prepared in the step of preparing the second monoblock polymer solution includes a polymer for forming a repeating unit block derived from a second vinyl aromatic monomer, which is the step of preparing the previous second monoblock polymer solution. Since the end of the polymer by polymerization is an anionic active living anionic polymer, the step of preparing the second diblock copolymer can be carried out without input of a separate polymerization initiator.
  • a polymerization reaction of a second conjugated diene-based monomer that is additionally introduced from the living anionic polymer is performed, and a third block including a repeating unit derived from a second vinyl aromatic monomer
  • a block according to the second conjugated diene-based monomer input in the step of preparing the second diblock copolymer may be a step for preparing the second diblock copolymer.
  • the second diblock copolymer contained in the second diblock copolymer solution prepared in the step of preparing the second diblock copolymer is coupled using a coupling agent.
  • the diblock copolymer may be a step for preparing a solution comprising a triblock copolymer coupled, that is, a block copolymer.
  • the second diblock copolymer solution prepared in the step of preparing the second diblock copolymer comprises a second diblock copolymer, which is copolymerized by polymerization in the step of preparing the second diblock copolymer.
  • the terminal specifically, the terminal of the block containing the repeating unit derived from the second conjugated diene monomer is an anionic active living anionic copolymer
  • the number of functional groups that can be substituted or added to the coupling agent is added. Accordingly, a coupling reaction in which the functional group of the second coupling agent is replaced with the living anionic copolymer or the living anionic copolymer is added to the functional group of the second coupling agent may be performed. That is, in the triblock copolymer, a second diblock copolymer may be connected by the coupling agent according to the number of functional groups that can be substituted or added in a coupling agent, and specific examples include two or more second diblocks.
  • the copolymer may be coupled by a coupling group derived from the coupling agent, and more specifically, 2 to 4 second diblock copolymers may be coupled by a coupling group derived from the coupling agent.
  • the step of preparing the triblock copolymer may further include, after the coupling reaction, removing the activity of the active polymer by adding water or alcohol into the reactor.
  • the hydrocarbon-based solvent does not react with a polymerization initiator, and can be used as long as it is usually used for anionic polymerization reactions.
  • Specific examples include butane, n-pentane, n-hexane, n-heptane or iso-octane.
  • Linear or branched aliphatic hydrocarbon compounds Cyclic aliphatic hydrocarbon compounds unsubstituted or substituted with alkyl groups such as cyclopentane, cyclohexane, cycloheptane, methyl cyclohexane or methyl cycloheptane; And it may be an aromatic hydrocarbon compound unsubstituted or substituted with an alkyl group such as benzene, toluene, xylene or naphthalene, any one of them, or a mixture of two or more.
  • alkyl groups such as cyclopentane, cyclohexane, cycloheptane, methyl cyclohexane or methyl cycloheptane
  • aromatic hydrocarbon compound unsubstituted or substituted with an alkyl group such as benzene, toluene, xylene or naphthalene, any one of them, or a mixture of two or more
  • the polymerization initiator used in the step of preparing the block copolymer may be one or more selected from the polymerization initiators described above.
  • the step of mixing the diblock copolymer and the triblock copolymer may be a step for preparing a block copolymer composition in which the diblock copolymer and the triblock copolymer are mixed with each other.
  • the mixing may be carried out by mixing in the form of a powder, respectively, in order to evenly distribute and distribute the diblock copolymer and the triblock copolymer in the block copolymer composition, respectively, comprising the diblock copolymer prepared in the above step It can be carried out by mixing the solution and the solution containing the triblock copolymer prepared in the above step, in this case, the dispersibility of the diblock copolymer and the triblock copolymer is excellent, and has a uniform distribution, block air There is an excellent effect of balance between the physical properties of the asphalt composition containing the coalescence composition.
  • an asphalt composition comprising an asphalt modifier for the block copolymer composition.
  • the asphalt composition may include the block copolymer composition and asphalt.
  • the block copolymer composition may be included in 1 part by weight to 10 parts by weight, 3 parts by weight to 8 parts by weight, or 4 parts by weight to 6 parts by weight based on 100 parts by weight of the total asphalt composition, within this range
  • the block copolymer composition has excellent solubility in asphalt, and has an excellent effect in physical properties of the asphalt composition.
  • the asphalt composition may further include a crosslinking agent for crosslinking the asphalt composition.
  • the crosslinking agent may be a sulfur compound containing sulfur or iron sulfate, a specific example may be a sulfur element (powder), and the crosslinking agent may be included in an amount of 0.05 to 3 parts by weight based on 100 parts by weight of the total asphalt composition, It maintains an appropriate crosslinking reaction within this range, improves high temperature properties and elasticity, and has an effect of preventing gelation.
  • the asphalt may include asphaltenes in an amount of 1 wt% to 40 wt%, or 5 wt% to 30 wt% based on the total weight of the asphalt.
  • the asphalt composition may be a road pavement material or a building material such as a waterproof material.
  • a diblock copolymer solution including a (butadiene)-(styrene) diblock copolymer substituted with a functional group derived from a modified initiator represented by the following Chemical Formula 2 was prepared.
  • Example 1 when preparing the diblock copolymer, instead of 1.965 g of N,N-dimethyl vinylbenzyl amine, 1.965 g of vinyl benzyl amine (primary amine) was added to prepare a solution containing a modified initiator represented by Formula 3 below. It was carried out in the same manner as in Example 1, except that it was prepared.
  • Example 1 when preparing the block copolymer composition, except that the diblock copolymer solution was used as 48 parts by weight instead of 33 parts by weight (based on solid content), instead of 52 parts by weight of triblock copolymer solution (based on solid content) was carried out in the same manner as in Example 1.
  • Example 1 when manufacturing the block copolymer composition, except that the diblock copolymer solution was used as 33 parts by weight (based on solids) instead of 16 parts by weight, triblock copolymer solution 67 parts by weight (based on solids) instead of 84 parts by weight was carried out in the same manner as in Example 1.
  • Example 1 when the block copolymer composition was prepared, the triblock copolymer solution was not used, and the diblock copolymer solution was used in the same manner as in Example 1, except that only 100 parts by weight (based on solids) was used. Did.
  • Example 1 when the block copolymer composition was prepared, the diblock copolymer solution was not used, and the triblock copolymer solution was used in the same manner as in Example 1, except that only 100 parts by weight (based on solids) was used. Did.
  • Comparative Example 3 when the triblock copolymer was prepared, Comparative Example 3 was used except that 26.05 g instead of 28.54 g of n-butyllithium diluted to 4% in cyclohexane and 0.75 g of 1.003 g of dimethyldichlorosilane were used. It was carried out in the same way.
  • Comparative Example 3 when the triblock copolymer was prepared, it was carried out in the same manner as in Comparative Example 3, except that 0.90 g was used instead of 1.003 g of dimethyldichlorosilane.
  • Comparative Example 3 when the triblock copolymer was prepared, Comparative Example 3 was used except that 28.54 g of n-butyllithium diluted in cyclohexane at 4% was used as 23.67 g, and 0.85 g instead of 1.003 g of dimethyldichlorosilane. It was carried out in the same way.
  • each block copolymer composition prepared in Examples 1 to 4 and Comparative Examples 1 to 6 as an asphalt modifier, to compare the softening point, viscosity, and phase separation temperature, asphalt at 180° C. (SK AP-5 ) 600 g of each block copolymer composition prepared in Examples 1 to 4 and Comparative Examples 1 to 6 was calculated and added at 4.5% by weight, and then 30 minutes at 2,500 rpm in a high shear stirrer (HSM, High Shear Mixer).
  • HSM High Shear stirrer
  • TSV viscosity (cSt) The block copolymer composition was dissolved in toluene at a concentration of 5% by weight and measured using a capillary viscometer in a constant temperature bath maintained at 25°C.
  • Coupling efficiency (%) ⁇ (area of coupled polymer)/(area of entire polymer) ⁇ X 100
  • Viscosity (cps) When preparing the asphalt composition, after 2 hours of low-shear stirring, the viscosity of 135° C. was measured using a Brookfield Viscometer (BROOK FIELD VISCOMETER).
  • Phase separation temperature (solubility ⁇ T, °C): 50 g of the prepared asphalt composition is improved in an aluminum tube, aged in an oven at 180° C. for 72 hours (aging), and then divided into three parts to determine the softening point of the upper and lower parts. It was measured in the same way. At this time, the lower the value of the phase separation temperature means that the solubility increases.
  • Comparative Example 1 containing only the diblock copolymer had a lower softening point
  • Comparative Example 2 containing only the triblock copolymer had a lower solubility
  • a block copolymer composition prepared by mixing a diblock copolymer and a triblock copolymer is a comparative example
  • the softening point is reduced (Comparative Examples 3 and 5) or the solubility confirmed at the phase separation temperature is lowered compared to the examples according to the present invention (Comparative Examples 4 and 6).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de copolymère bloc. Plus spécifiquement, la présente invention concerne : une composition de copolymère bloc contenant un copolymère dibloc et un copolymère tribloc, le copolymère dibloc comprenant un premier bloc contenant une unité de répétition dérivée d'un premier monomère à base de diène conjugué et un second bloc contenant une unité de répétition dérivée d'un premier monomère aromatique de vinyle, et une extrémité du copolymère dibloc contenant un groupe fonctionnel dérivé d'un initiateur modifié représenté par la formule chimique 1 (voir description de l'invention) ; un procédé de production de la composition de copolymère séquencé ; et une composition d'asphalte comprenant la composition de copolymère séquencé.
PCT/KR2019/015945 2018-11-26 2019-11-20 Composition de copolymère bloc, son procédé de production et composition d'asphalte la contenant WO2020111644A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2020545475A JP6995213B2 (ja) 2018-11-26 2019-11-20 ブロック共重合体組成物、その製造方法、およびそれを含むアスファルト組成物
US16/978,062 US11203687B2 (en) 2018-11-26 2019-11-20 Block copolymer composition, method of preparing the same, and asphalt composition including the same
EP19891032.5A EP3744787B1 (fr) 2018-11-26 2019-11-20 Composition de copolymère bloc, son procédé de production et composition d'asphalte la contenant
CN201980017218.9A CN111819241B (zh) 2018-11-26 2019-11-20 嵌段共聚物组合物，其制备方法以及包含其的沥青组合物

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KR10-2018-0147745 2018-11-26
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KR1020190139439A KR102241925B1 (ko) 2018-11-26 2019-11-04 블록 공중합체 조성물, 이의 제조방법 및 이를 포함하는 아스팔트 조성물

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JP2002060583A (ja) * 2000-08-11 2002-02-26 Katon Jsr Elastomer Kk アスファルト改質用共重合体（組成物）、およびアスファルト組成物
KR20090052767A (ko) * 2007-11-21 2009-05-26 금호석유화학 주식회사 스티렌계 복합 블록 공중합체 혼합물의 제조방법 및 이를함유한 개질 아스팔트 조성물
KR20160052310A (ko) * 2014-11-04 2016-05-12 주식회사 엘지화학 아스팔트 개질제 및 이를 포함하는 아스팔트 조성물
US20170210841A1 (en) * 2016-01-26 2017-07-27 Dynasol Elastómeros, S.A. De C.V. Counter Tapered Thermoplastic Elastomers
KR20180043535A (ko) * 2016-10-20 2018-04-30 주식회사 엘지화학 음이온 중합개시제의 제조방법, 이의 제조장치 및 이로부터 제조되는 음이온 중합개시제 조성물

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US5567815A (en) * 1994-07-18 1996-10-22 Bridgestone Corporation Teritary amine containing antonic initiators used in preparing polymers and process for the preparation thereof
JP2002060583A (ja) * 2000-08-11 2002-02-26 Katon Jsr Elastomer Kk アスファルト改質用共重合体（組成物）、およびアスファルト組成物
KR20090052767A (ko) * 2007-11-21 2009-05-26 금호석유화학 주식회사 스티렌계 복합 블록 공중합체 혼합물의 제조방법 및 이를함유한 개질 아스팔트 조성물
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US20170210841A1 (en) * 2016-01-26 2017-07-27 Dynasol Elastómeros, S.A. De C.V. Counter Tapered Thermoplastic Elastomers
KR20180043535A (ko) * 2016-10-20 2018-04-30 주식회사 엘지화학 음이온 중합개시제의 제조방법, 이의 제조장치 및 이로부터 제조되는 음이온 중합개시제 조성물

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